The Effect of Processing Conditions on the Microstructure of Homopolymer High-Density Polyethylene Blends: A Multivariate Approach.

In this work, a multivariate approach was utilized for gaining some insights into the processing-structure-properties relationships in polyethylene-based blends. In particular, two high-density polyethylenes (HDPEs) with different molecular weights were melt-compounded using a twin-screw extruder, and the effects of the screw speed, processing temperature and composition on the microstructure of the blends were evaluated based on a Design of Experiment-multilinear regression (DoE-MLR) approach. The results of the thermal characterization, interpreted trough the MLR (multilinear regression) response surfaces, demonstrated that the composition of the blends and the screw rotation speed are the two most important parameters in determining the crystallinity of the materials. Furthermore, the rheological data were examined using a Principal Component Analysis (PCA) multivariate approach, highlighting also in this case the most prominent effect of the weight ratio of the two base polymers and the screw rotation speed.

Development of a Polypropylene-Based Material with Flame-Retardant Properties for 3D Printing.

In this study, a nanocomposite based on a heterophasic polypropylene copolymer containing 5 wt% of nanoclays and 3 wt% of compatibilizer was formulated via melt compounding to obtain a material suitable for Fused Filament Fabrication (FFF) processing with enhanced flame-retardant properties. From rheological analyses, the nanocomposite showed an important increase in the non-Newtonian behavior, and, therefore, improved FFF printability compared to the pristine PP COPO. A filament with suitable characteristics for FFF was produced using a single-screw extruder and subsequently 3D printed. Finally, cone calorimeter and UL94 tests were carried out on both 3D-printed and compression-molded specimens. The obtained results showed that the 3D-printed samples exhibited even better flame-retardant properties than the compression-molded ones, thus demonstrating not only the possibility of successfully developing and using functionalized PP-based filaments in 3D printing but also the possibility of obtaining enhanced flame-retardant properties compared to conventional compression molding.

Optimizing the Rheological and Thermal Behavior of Polypropylene-Based Composites for Material Extrusion Additive Manufacturing Processes.

In this study, composites based on a heterophasic polypropylene (PP) copolymer containing different loadings of micro-sized (i.e., talc, calcium carbonate, and silica) and nano-sized (i.e., a nanoclay) fillers were formulated via melt compounding to obtain PP-based materials suitable for Material Extrusion (MEX) additive manufacturing processing. The assessment of the thermal properties and the rheological behavior of the produced materials allowed us to disclose the relationships between the influence of the embedded fillers and the fundamental characteristics of the materials affecting their MEX processability. In particular, composites containing 30 wt% of talc or calcium carbonate and 3 wt% of nanoclay showed the best combination of thermal and rheological properties and were selected for 3D printing processing. The evaluation of the morphology of the filaments and the 3D-printed samples demonstrated that the introduction of different fillers affects their surface quality as well as the adhesion between subsequently deposited layers. Finally, the tensile properties of 3D-printed specimens were assessed; the obtained results showed that modulable mechanical properties can be achieved depending on the type of the embedded filler, opening new perspectives towards the full exploitation of MEX processing in the production of printed parts endowed with desirable characteristics and functionalities.

Identification of Plastics in Mixtures and Blends through Pyrolysis-Gas Chromatography/Mass Spectrometry.

In this paper, the possibility of detecting polymers in plastic mixtures and extruded blends has been investigated. Pyrolysis-gas chromatography/mass spectrometry (py-GC/MS) allows researchers to identify multicomponent mixtures and low amounts of polymers without high spatial resolution, background noise and constituents mix interfering, as with molecular spectrometry techniques normally used for this purpose, such as Fourier transform infrared spectroscopy (FTIR) and Raman spectroscopy and differential scanning calorimetry (DSC). In total, 15 solid mixtures of low-density polyethylene (LDPE), polypropylene (PP), polystyrene (PS), polyamide (PA) and polycarbonate (PC) in various combinations have been qualitatively analyzed after choosing their characteristic pyrolysis products and each polymer has been detected in every mix; thus, in extruded blends of high-density polyethylene (HDPE), PP and PS had varying weight percentages of the individual constituents ranging from 10 up to 90. Moreover, quantitative analysis of these polymers has been achieved in every blend with a trend that can be considered linear with coefficients of determination higher than 0.9, even though the limits of quantification are lower with respect to the ones reported in the literature, probably due to the extrusion process.

Evolution of the Microstructure of PP-LDHs Nanocomposites during Melt Compounding: A Simulation Approach.

In the context of polymer-based nanocomposites containing layered nanofillers, the achievement of good extents of dispersion and distribution of the embedded nanoparticles and, even more, the obtainment of intercalated and/or exfoliated structures through melt compounding still represents a persistent challenge, especially in the case of anionic layered double hydroxides (LDHs)-containing systems and non-polar polymeric matrices. In this work, a simulation approach is proposed to evaluate the influence of the processing conditions on the morphology of polypropylene (PP)-based nanocomposites containing organomodified LDHs. In particular, the effect of the screw rotation speed and the feed rate on the final microstructure of the materials formulated through melt compounding in a twin-screw extruder was assessed. The rheological and morphological characterizations demonstrated that a more homogeneous morphology was achieved when high levels of both exploited processing parameters are selected. The results coming from the simulation of the processing were used to establish some relationships between the flow parameters and the microstructure of the nanocomposites, demonstrating that low residence times coupled with high local shear rates are required to ensure the achievement of homogenous morphologies, likely involving the occurrence of intercalation phenomena.

Improvement of Poly(lactic acid)-Poly(hydroxy butyrate) Blend Properties for Use in Food Packaging: Processing, Structure Relationships.

Poly(lactic acid)-poly(hydroxybutyrate) (PLA-PHB)-based nanocomposite films were prepared with bio-based additives (CNCs and ChNCs) and oligomer lactic acid (OLA) compatibilizer using extrusion and then blown to films at pilot scale. The aim was to identify suitable material formulations and nanocomposite production processes for film production at a larger scale targeting food packaging applications. The film-blowing process for both the PLA-PHB blend and CNC-nanocomposite was unstable and led to non-homogeneous films with wrinkles and creases, while the blowing of the ChNC-nanocomposite was stable and resulted in a smooth and homogeneous film. The optical microscopy of the blown nanocomposite films indicated well-dispersed chitin nanocrystals while the cellulose crystals were agglomerated to micrometer-size particles. The addition of the ChNCs also resulted in the improved mechanical performance of the PLA-PHB blend due to well-dispersed crystals in the nanoscale as well as the interaction between biopolymers and the chitin nanocrystals. The strength increased from 27 MPa to 37 MPa compared to the PLA-PHB blend and showed almost 36 times higher elongation at break resulting in 10 times tougher material. Finally, the nanocomposite film with ChNCs showed improved oxygen barrier performance as well as faster degradation, indicating its potential exploitation for packaging applications.

FDM Printability of PLA Based-Materials: The Key Role of the Rheological Behavior.

Fused deposition modeling (FDM) is one of the most commonly used commercial technologies of materials extrusion-based additive manufacturing (AM), used for obtaining 3D-printed parts using thermoplastic polymers. Notwithstanding the great variety of applications for FDM-printed objects, the choice of materials suitable for processing using AM technology is still limited, likely due to the lack of rapid screening procedures allowing for an efficient selection of processable polymer-based formulations. In this work, the rheological behavior of several 3D-printable, commercially available poly(lactic acid)-based filaments was accurately characterized. In particular, each step of a typical FDM process was addressed, from the melt flowability through the printing nozzle, to the interlayer adhesion in the post-deposition stage, evaluating the ability of the considered materials to fulfill the criteria for successful 3D printing using FDM technology. Furthermore, the rheological features of the investigated materials were related to their composition and microstructure. Although an exhaustive and accurate evaluation of the 3D printability of thermoplastics must also consider their thermal behavior, the methodology proposed in this work aimed to offer a useful tool for designing thermoplastic-based formulations that are able to ensure an appropriate rheological performance in obtaining 3D-printed parts with the desired geometry and final properties.

Anaerobic digestion and aerobic composting of rigid biopolymers in bio-waste treatment: fate and effects on the final compost.

Bioplastics may be collected in the bio-waste treatment, which is often composed of anaerobic digestion and subsequent aerobic composting of the digestates. The aim of this study was to evaluate the degradability of polylactic acid (PLA) and starch-based bioplastics (SBB) spoons under industrial conditions. Biomethane potential (BMP) was measured and biogas production was monitored, while the quality of composts was assessed by phytotoxicity and ecotoxicity tests. The bioplastics disintegration resulted in 65.1 ± 4.6 % for PLA and ≤ 65.0 ± 7.4 % for SBB, not achieving the target set by UNI EN 13,432 standard, and several residues were found in compost. Phytotoxicity tests on seeds reported the lowest Germination Index for PLA elutriate, whereas a potential negative effect of SBB on soil fauna was detected. Further investigation is needed to assess the fate of these ever-growing materials under industrial conditions, and also evaluate the effects of residues in compost.

Effects of the Manufacturing Methods on the Mechanical Properties of a Medical-Grade Copolymer Poly(L-lactide-co-D,L-lactide) and Poly(L-lactide-co-ε-caprolactone) Blend.

Biocompatible and biodegradable polymers represent the future in the manufacturing of medical implantable solutions. As of today, these are generally manufactured with metallic components which cannot be naturally absorbed within the human body. This requires performing an additional surgical procedure to remove the remnants after complete rehabilitation or to leave the devices in situ indefinitely. Nevertheless, the biomaterials used for this purpose must satisfy well-defined mechanical requirements. These are difficult to ascertain at the design phase since they depend not only on their physicochemical properties but also on the specific manufacturing methods used for the target application. Therefore, this research was focused on establishing the effects of the manufacturing methods on both the mechanical properties and the thermal behavior of a medical-grade copolymer blend. Specifically, Injection and Compression Molding were considered. A Poly(L-lactide-co-D,L-lactide)/Poly(L-lactide-co-ε-caprolactone) blend was considered for this investigation, with a ratio of 50/50 (w/w), aimed at the manufacturing of implantable devices for tendon repair. Interesting results were obtained.

Investigation of Different Types of Biochar on the Thermal Stability and Fire Retardance of Ethylene-Vinyl Acetate Copolymers.

In this work, three biochars, deriving from soft wood, oil seed rape, and rice husk and differing as far as the ash content is considered (2.3, 23.4, and 47.8 wt.%, respectively), were compounded in an ethylene vinyl acetate copolymer (vinyl acetate content: 19 wt.%), using a co-rotating twin-screw extruder; three loadings for each biochar were selected, namely 15, 20, and 40 wt.%. The thermal and mechanical properties were thoroughly investigated, as well as the flame retardance of the resulting compounds. In particular, biochar, irrespective of the type, slowed down the crystallization of the copolymer: this effect increased with increasing the filler loading. Besides, despite a very limited effect in flammability tests, the incorporation of biochar at increasing loadings turned out to enhance the forced-combustion behavior of the compounds, as revealed by the remarkable decrease of peak of heat release rate and of total heat release, notwithstanding a significant increase of the residues at the end of the tests. Finally, increasing the biochar loadings promoted an increase of the stiffness of the resulting compounds, as well as a decrease of their ductility with respect to unfilled ethylene vinyl acetate (EVA), without impacting too much on the overall mechanical behavior of the copolymer. The obtained results seem to indicate that biochar may represent a possible low environmental impact alternative to the already used flame retardants for EVA, providing a good compromise between enhanced fire resistance and acceptable mechanical properties.

Dielectric Spectroscopy of PP/MWCNT Nanocomposites: Relationship with Crystalline Structure and Injection Molding Condition.

In this paper, we study the correlation between the dielectric behavior of polypropylene/multi-walled carbon nanotube (PP/MWCNT) nanocomposites and the morphology with regard to the crystalline structure, nanofiller dispersion and injection molding conditions. As a result, in the range of the percolation threshold the dielectric behavior shifts to a more frequency-independent behavior, as the mold temperature increases. Moreover, the position further from the gate appears as the most conductive. This effect has been associated to a modification of the morphology of the MWCNT clusters induced by both the flow of the molten polymer during the processing phase and the variation of the crystalline structure, which is increasingly constituted by γ-phase as the mold temperature increases. The obtained results allow one to understand the effect of tuning the processing condition in the frequency-dependent electrical behavior of PP/MWCNT injection-molded nanocomposites, which can be successfully exploited for an advanced process/product design.

PET Foams Surface Treated with Graphene Nanoplatelets: Evaluation of Thermal Resistance and Flame Retardancy.

In this work, fire-retardant systems consisting of graphene nanoplatelets (GNPs) and dispersant agents were designed and applied on polyethylene terephthalate (PET) foam. Manual deposition from three different liquid solutions was performed in order to create a protective coating on the specimen's surface. A very low amount of coating, between 1.5 and 3.5 wt%, was chosen for the preparation of coated samples. Flammability, flame penetration, and combustion tests demonstrated the improvement provided to the foam via coating. In particular, specimens with PSS/GNPs coating, compared to neat foam, were able to interrupt the flame during horizontal and vertical flammability tests and led to longer endurance times during the flame penetration test. Furthermore, during cone calorimetry tests, the time to ignition (TTI) increased and the peak of heat release rate (pHRR) was drastically reduced by up to 60% compared to that of the uncoated PET foam. Finally, ageing for 48 and 115 h at 160 °C was performed on coated specimens to evaluate the effect on flammability and combustion behavior. Scanning electron microscopy (SEM) images proved the morphological effect of the heat treatment on the surface, showing that the coating was uniformly distributed. In this case, fire-retardant properties were enhanced, even if fewer GNPs were used.

Is it Possible to Mechanical Recycle the Materials of the Disposable Filtering Masks?

In a singular period, such as during a pandemic, the use of personal protective masks can become mandatory for all citizens in many places worldwide. The most used device is the disposable mask that, inevitably, generates a substantial waste flow to send to incineration or landfill. The article examines the most diffused type of disposable face mask and identifies the characteristic of the constituent materials through morphological, chemical, physical, and thermal analyses. Based on these investigations, a mechanical recycling protocol with different approaches is proposed. Advantages and disadvantages of the different recycling solutions are discussed with considerations on necessary separation processes and other treatments. The four solutions investigated lead to a recycling index from 78 to 91% of the starting disposable mask weight. The rheological, mechanical, and thermo-mechanical properties of the final materials obtained from the different recycling approaches are compared with each other and with solutions present on the market resulting in materials potentially industrially exploitable.

Improving Fire Performances of PEAL: More Second-Life Options for Recycled Tetra Pak®.

The purpose of this work was to evaluate and improve the flammability and combustion behavior of the polyethylene-based material obtained from the recycling of Tetra Pak® (PEAL) to widen its use to applications where these properties are required. Firstly, its thermal stability was investigated with thermogravimetric analysis, resulting in an enhancement in the main degradation step temperature (from 385 °C to 421 °C) due to the presence of the aluminum-flakes. Then, to improve the poor flammability (HB in UL-94 test) and combustion behavior (Fire Performance Index of 0.07) of the raw material, two flame retardant approaches were tested: an intumescent system made of ammonium polyphosphate and pentaerythritol, and magnesium hydroxide. In addition, the effectiveness of polyethylene as a charring agent was evaluated. Characterization was made with UL-94, cone calorimeter, and morphologic analysis. For all the materials tested, the temperature of the main weight loss step increased and the flammability rating improved (V2 for intumescent and V0 for magnesium hydroxide reached). Moreover, fire hazard decreased (Fire Performance Index of 0.15 and 0.55; Flame Retardancy Index of 2.6 and 10.0). Referring to the morphology, full compatibility was found in the PEAL-magnesium hydroxide compound, while PEAL-intumescent appeared as a heterogeneous system.

Effect of Injection Molding Conditions on Crystalline Structure and Electrical Resistivity of PP/MWCNT Nanocomposites.

Polypropylene (PP) / multi-walled carbon nanotube (MWCNT) nanocomposites were prepared by melt-mixing and used to manufacture samples by injection molding. The effect of processing conditions on the crystallinity and electrical resistivity was studied. Accordingly, samples were produced varying the mold temperature and injection rate, and the DC electrical resistivity was measured. The morphology of MWCNT clusters was studied by optical and electron microscopy, while X-ray diffraction was used to study the role of the crystalline structure of PP. As a result, an anisotropic electrical behavior induced by the process was observed, which is further influenced by the injection molding processing condition. It was demonstrated that a reduction of electrical resistivity can be obtained by increasing mold temperature and injection rate, which was associated to the formation of the γ-phase and the related inter-cluster morphology of the MWCNT conductive network.

Development of Pressure-Responsive PolyPropylene and Biochar-Based Materials.

In this research paper, we reported the synthesis of biochar-based composites using biochar derived from exhausted tea leaves and polypropylene. The resulting materials were deeply characterized investigating mechanical (dynamic mechanical thermal analysis), thermal (thermogravimetrical analysis and differential scanning calorimetry), morphological (field emission scanning microscopy) and electrical properties vs. temperature. Furthermore, electrical conductivity was studied for a wide range of pressures showing an irreversible plastic deformation. An increment of one order of magnitude in the conductivity was observed in the case of 40 wt% biochar loading, reaching a value of 0.2 S/m. The material produced exhibited the properties of an irreversible pressure sensor.

Selective bacterial colonization processes on polyethylene waste samples in an abandoned landfill site.

The microbial colonization of plastic wastes has been extensively studied in marine environments, while studies on aged terrestrial wastes are scarce, and mostly limited to the isolation of plastic-degrading microorganisms. Here we have applied a multidisciplinary approach involving culturomics, next-generation sequencing analyses and fine-scale physico-chemical measurements to characterize plastic wastes retrieved in landfill abandoned for more than 35 years, and to assess the composition of bacterial communities thriving as biofilms on the films' surfaces. All samples were characterized by different colors but were all of polyethylene; IR and DSC analyses identified different level of degradation, while FT-Raman spectroscopy and X-ray fluorescence further assessed the degradation level and the presence of pigments. Each plastic type harbored distinct bacterial communities from the others, in agreement with the differences highlighted by the physico-chemical analyses. Furthermore, the most degraded polyethylene films were found to host a bacterial community more similar to the surrounding soil as revealed by both α- and ß-diversity NGS analyses. This work confirms the novel hypothesis that different polyethylene terrestrial waste samples select for different bacterial communities, and that structure of these communities can be correlated with physico-chemical properties of the plastics, including the degradation degree.

PLA/PHB Blends: Biocompatibilizer Effects.

The purpose of this work was to formulate a fully bio-based blend with superior properties, based on two immiscible polymers: polylactic acid (PLA) and poly-hydroxy butyrate (PHB). To improve the miscibility between the polymeric phases, two different kinds of compatibilizers with a different chemical structure were used, namely, an ethylene oxide/propylene oxide block copolymer in the form of flakes and a mixture of two liquid surfactants with a variable lipophilic-hydrophilic index. The morphology of the blends and their thermal, mechanical, and rheological behavior were evaluated, aiming at assessing the influence of the selected compatibilizers on the microstructure and final properties of the systems. Morphological analyses of the compatibilized blends indicated that the liquid surfactant is more effective than the solid copolymer in inducing morphology refinement, as also suggested by results coming from rheological measurements. Furthermore, thermal analyses demonstrated that the presence of both kinds of compatibilizers induced an enhancement of the crystallinity content of blends. Finally, a remarkable increase of the elastic modulus values was obtained for the compatibilized blends as compared to the pure counterparts, with a consequent significant enhancement of the HDT values.

Flame Retardant Effect of Nano Fillers on Polydimethylsiloxane Composites.

Polydimethylsiloxane has exceptional fire retardancy characteristics, which make it a popular polymer in flame retardancy applications. Flame retardancy of polydimethylsiloxane with different nano fillers was studied. Polydimethylsiloxane composite fire property varies because of the shape, size, density, and chemical nature of nano fillers. In house made carbon and bismuth oxide nano fillers were used in polydimethylsiloxane composite. Carbon from biochar (carbonised bamboo) and a carbon by-product (carbon soot) were selected. For comparative study of nano fillers, standard commercial multiwall carbon nano tubes (functionalised, graphitised and pristine) as nano fillers were selected. Nano fillers in polydimethylsiloxane positively affects their fire retardant properties such as total smoke release, peak heat release rate, and time to ignition. Charring and surface ceramization are the main reasons for such improvement. Nano fillers in polydimethylsiloxane may affect the thermal mobility of polymer chains, which can directly affect the time to ignition. The study concludes that the addition of pristine multiwall carbon nano tubes and bismuth oxide nano particles as filler in polydimethylsiloxane composite improves the fire retardant property.

Improving the Flame Retardant Efficiency of Layer by Layer Coatings Containing Deoxyribonucleic Acid by Post-Diffusion of Hydrotalcite Nanoparticles.

This work deals with the use of hydrotalcite nanoparticle post-diffusion in layer by layer (LbL) coatings with the aim of improving their flame retardant action on cotton. The selected LbL components, which encompass polydiallyldimethylammonium chloride and deoxyribonucleic acid, aim at the deposition of an intumescent coating. Infrared spectra pointed out a super-linear growth of the investigated assembly, indicating the ability to deposit thick coatings while maintaining a relatively low deposition number. A post-diffusion process, performed by exposing the LbL-treated fabrics to two different concentrations of hydrotalcite water suspensions (0.1 or 1 wt %), was carried out to improve the fireproofing efficiency of these coatings. Coatings treated with the lowest concentration suspension partially swelled as a consequence of their structural rearrangements while the use of the highest concentration led to nanoparticle aggregates. Horizontal flame spread tests were used for assessing the achieved flame retardant properties. The post-diffusion performed at the lowest hydrotalcite concentration lowers the minimum number of Bi-Layers required for obtaining cotton self-extinguishment while samples treated with the highest concentration showed detrimental effects on the performances of treated fabrics. This behavior is ascribed to the effects of hydrotalcite particles on the intumescence of LbL coatings, as evidenced by the morphological analyses of post-combustion residues.